Modified epoxy resin as well as preparation method and application thereof

Abstract

The invention discloses modified epoxy resin as well as a preparation method and application thereof. The modified epoxy resin comprises the following raw materials: epoxy resin, benzoxazine resin, cyanate ester resin, a curing agent and a catalyst, wherein the mass ratio of the epoxy resin to the benzoxazine resin to the cyanate ester resin is 6: (1-3): (1-3); the mass ratio of the curing agent to the epoxy resin is (0.02-0.05): 1; the mass ratio of the catalyst to the epoxy resin is (0.001-0.005): 1. The modified epoxy resin disclosed by the invention is good in thermal stability and high in Tg, can meet the use requirements in a high-temperature environment, and is also relatively excellent in brittleness.

Description

Technical Field

[0001] The invention relates to a modified epoxy resin and a preparation method and application thereof. Background Art

[0002] At present, electronic products are developing towards high frequency and high speed, and at the same time, the requirements for reliability are getting higher and higher. For copper clad laminates as substrate materials, they are increasingly required to have high heat resistance.

[0003] Epoxy resin has strong reactivity and adhesion because of the epoxy and hydroxyl groups in its molecular structure. Its curing process is addition polymerization, and the cured product does not produce water and other low molecular weight substances, so the shrinkage rate of the cured product is small. The cured product has high mechanical strength, excellent chemical resistance and dielectric properties. In addition, its price is moderate, so epoxy resin is widely used in the production of copper clad laminates.

[0004] At present, the epoxy resins commonly used in the copper clad laminate industry include bisphenol A epoxy resin, linear phenolic epoxy resin, brominated epoxy resin and bisphenol S epoxy resin. However, although epoxy resin has excellent comprehensive performance, it can no longer meet the requirements of reliability and heat resistance of high-end copper clad laminates in the current market. Therefore, we need to modify the resin to increase its Tg (Tg is also called glass transition temperature, which refers to the temperature at which polymers change from glass state to high elastic state. Tg directly affects the process performance and use performance of the material. At the glass transition temperature, the expansion coefficient, thermal conductivity and dielectric constant of polymers may change.) The glass transition temperature of copper clad laminates with ordinary epoxy resin systems is generally between 130-140℃, and its thermal expansion coefficient in the Z-axis direction is large, and its heat resistance is low. Especially when the plate exceeds the Tg temperature, the performance of each performance drops significantly, limiting its use in high temperature environments. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the defect that the glass transition temperature (Tg) of epoxy resin in the prior art is low and cannot meet the use requirements of high temperature environment, and provide a modified epoxy resin and its preparation method and application. The modified epoxy resin of the present invention has good thermal stability and high Tg, which can meet the use requirements of high temperature environment. At the same time, the modified epoxy resin of the present application is also relatively excellent in brittleness.

[0006] The technical problem to be solved by the present invention is achieved through the following technical solutions.

[0007] The present invention provides a modified epoxy resin, the raw materials of which include epoxy resin, benzoxazine resin and cyanate resin, a curing agent and a catalyst;

[0008] Wherein, the mass ratio of the epoxy resin, the benzoxazine resin and the cyanate resin is 6:(1-3):(1-3);

[0009] Wherein, the mass ratio of the curing agent to the epoxy resin is (0.02-0.05): 1;

[0010] Wherein, the mass ratio of the catalyst to the epoxy resin is (0.001-0.005):1.

[0011] In the present invention, the modified epoxy resin exists in the form of glue, for example.

[0012] In the present invention, preferably, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, resorcinol epoxy resin, polyethylene glycol epoxy resin, brominated epoxy resin, isocyanate modified epoxy resin, rubber modified epoxy resin, glycidylamine epoxy resin and phosphorus-containing epoxy resin, such as bisphenol A epoxy resin.

[0013] In the present invention, preferably, the benzoxazine resin is selected from one or more of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, MDA type benzoxazine resin, DCPD type benzoxazine resin, phenol type benzoxazine resin, DOPO type benzoxazine resin, phenolphthalein type benzoxazine resin, bisphenol AF type benzoxazine resin, furfurylamine type benzoxazine resin and aniline type benzoxazine resin, such as bisphenol A type benzoxazine resin.

[0014] In the present invention, preferably, the cyanate ester resin is selected from bisphenol A type cyanate ester resin.

[0015] In the present invention, preferably, the curing agent is selected from one or more of dicyandiamide (DICY), m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, dichlorodiaminodiphenylmethane, phenol novolac resin, bisphenol A novolac resin, phosphorus-containing phenolic resin, benzoxazine resin, xylene formaldehyde resin, urea-formaldehyde resin, modified phenolic resin, maleic anhydride and styrene maleic anhydride copolymer, such as dicyandiamide.

[0016] In the present invention, preferably, the catalyst is selected from one or more of imidazole compounds, benzyldimethylamine, 2,4,6-tris(dimethylaminomethylamine)phenol, and boron trifluoride.

[0017] The imidazole compound is, for example, 2-methylimidazole (2-MI).

[0018] In the present invention, the mass ratio of the epoxy resin, the benzoxazine resin and the cyanate resin is, for example, (6:3:1), (3:1:1) or (6:1:3).

[0019] In the present invention, the mass ratio of the curing agent to the epoxy resin is, for example, 0.035:1.

[0020] In the present invention, the mass ratio of the catalyst to the epoxy resin is, for example, 0.002:1.

[0021] In the present invention, preferably, the raw materials of the modified epoxy resin further include inorganic fillers and / or organic solvents.

[0022] Among them, preferably, the inorganic filler is selected from one or more of silicon dioxide, calcium oxide, magnesium oxide, aluminum oxide, boron oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, talc, calcium carbonate, mica powder, kaolin, magnetic powder and quartz powder, such as aluminum oxide.

[0023] Preferably, the mass ratio of the inorganic filler to the epoxy resin is (0.3-0.7):1, for example, 0.5:1.

[0024] Preferably, the organic solvent is selected from one or more of acetone, butanone, N,N-dimethylformamide (DMF), ethylene glycol methyl ether, propylene glycol methyl ether, such as N,N-dimethylformamide.

[0025] Preferably, the mass ratio of the organic solvent to the epoxy resin is (0.5-0.8):1, for example, 0.67:1.

[0026] In the present invention, preferably, the raw materials of the modified epoxy resin include or consist of the following formula in parts by mass:

[0027] 60 parts of epoxy resin,

[0028] 10-30 parts of benzoxazine resin,

[0029] 10-30 parts of cyanate resin,

[0030] 1-3 parts of curing agent,

[0031] Catalyst 0.05-0.2 parts,

[0032] More preferably, the raw materials of the modified epoxy resin include or consist of the following formula in parts by mass:

[0033] 60 parts of bisphenol A epoxy resin,

[0034] 10-30 parts of bisphenol A type benzoxazine resin,

[0035] 10-30 parts of bisphenol A cyanate resin,

[0036] 1-3 parts of curing agent,

[0037] Catalyst 0.05-0.2 parts;

[0038] Further preferably, the raw materials of the modified epoxy resin include or consist of the following formula in parts by mass:

[0039] 60 parts of bisphenol A epoxy resin,

[0040] 10-30 parts of bisphenol A type benzoxazine resin,

[0041] 10-30 parts of bisphenol A cyanate resin,

[0042] 1-3 parts of curing agent,

[0043] Catalyst 0.05-0.2 parts,

[0044] 20-40 parts of inorganic filler,

[0045] 20-40 parts of organic solvent.

[0046] In a specific embodiment of the present invention, the raw materials of the modified epoxy resin and the amount thereof are selected from one of the following schemes in terms of mass fractions:

[0047] Solution 1:

[0048] 60 parts of bisphenol A epoxy resin,

[0049] 30 parts of bisphenol A type benzoxazine resin,

[0050] 10 parts of bisphenol A cyanate resin,

[0051] 2.1 parts of dicyandiamide,

[0052] 0.12 parts of 2-methylimidazole,

[0053] 30 parts of aluminum oxide,

[0054] 40 parts of N,N-dimethylformamide;

[0055] Option 2:

[0056] 60 parts of bisphenol A epoxy resin,

[0057] 20 parts of bisphenol A type benzoxazine resin,

[0058] 20 parts of bisphenol A cyanate resin,

[0059] 2.1 parts of dicyandiamide,

[0060] 0.12 parts of 2-methylimidazole,

[0061] 30 parts of aluminum oxide,

[0062] 40 parts of N,N-dimethylformamide;

[0063] Option 3:

[0064] 60 parts of bisphenol A epoxy resin,

[0065] 10 parts of bisphenol A type benzoxazine resin,

[0066] 30 parts of bisphenol A cyanate resin,

[0067] 2.1 parts of dicyandiamide,

[0068] 0.12 parts of 2-methylimidazole,

[0069] 30 parts of aluminum oxide,

[0070] 40 parts of N,N-dimethylformamide.

[0071] The present invention provides a method for preparing a modified epoxy resin, which comprises the following steps:

[0072] Mixing raw materials for preparing the modified epoxy resin, wherein the raw materials include epoxy resin, benzoxazine resin, cyanate resin, curing agent and catalyst;

[0073] Wherein, the mass ratio of the epoxy resin, the benzoxazine resin and the cyanate resin is 6:(1-3):(1-3);

[0074] Wherein, the mass ratio of the curing agent to the epoxy resin is (0.02-0.05): 1;

[0075] Wherein, the mass ratio of the catalyst to the epoxy resin is (0.001-0.005):1.

[0076] In the present invention, preferably, the types and amounts of the epoxy resin, the benzoxazine resin, the cyanate resin, the curing agent and the catalyst are as described above.

[0077] In the present invention, preferably, the raw material further comprises an inorganic filler and / or an organic solvent, and the type and amount of the inorganic filler and / or the organic solvent are as described above.

[0078] In the present invention, preferably, the curing agent and the catalyst in the raw material are in a dissolved state. More preferably, under a 40-100 times microscope, the number of the curing agent crystals in the field of view of 1 mL of the solution A is less than 3.

[0079] In the present invention, preferably, the mixing is stirring, for example, stirring for 4-6 hours.

[0080] In the present invention, preferably, the preparation method further comprises: after mixing the epoxy resin, the benzoxazine resin, the cyanate resin, the curing agent and the catalyst, adding an inorganic filler, high shear emulsification and aging.

[0081] The high shear emulsification time is, for example, 5-10 minutes.

[0082] The aging time is, for example, 8-16 hours.

[0083] In the present invention, the modified epoxy resin exists in the form of glue, for example.

[0084] The present invention also provides a modified epoxy resin, which is prepared by the above-mentioned preparation method of the modified epoxy resin.

[0085] The present invention also provides a use of the modified epoxy resin as described above in preparing a copper clad laminate.

[0086] In the present invention, preferably, the method for preparing the copper clad laminate comprises the following steps:

[0087] The modified epoxy resin as described above is coated on a glass fiber cloth, and after being subjected to baking and pressing processes, a copper clad laminate is obtained.

[0088] Preferably, the mass per square meter of the glass fiber cloth is 40-300 g / m 2 .

[0089] Preferably, the glass fiber cloth is electronic grade glass fiber cloth.

[0090] On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0091] The reagents and raw materials used in the present invention are commercially available.

[0092] The positive and progressive effects of the present invention are:

[0093] The modified epoxy resin of the present invention has good thermal stability and high Tg, and can meet the use requirements in high temperature environments. At the same time, the modified epoxy resin of the present application also has excellent brittleness. DETAILED DESCRIPTION

[0094] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0095] In the specific implementation manner of the present invention, the main reagents or instruments used are shown in Table 1. The reagents or instruments whose specific sources are not indicated in the following examples are selected according to routine practices.

[0096] Table 1

[0097]

[0098] Example 1

[0099] Embodiment 1 provides a modified epoxy resin, and its preparation method is as follows:

[0100] According to the amount of Example 1 in Table 2, dicyandiamide (DICY), 2-methylimidazole (2-MI), and dimethylformamide (DMF) are added to a 500 ml beaker, and stirred for about 2 hours using a stirrer. After fully stirring and dissolving, 1 ml of the solution is extracted and the number of dicyandiamide crystals is observed under a 40-100 times microscope. When there are less than 3 dicyandiamide crystals in the field of view, it is qualified. After passing the test, bisphenol A epoxy resin, bisphenol A cyanate resin, and bisphenol A benzoxazine resin are added to the beaker in turn, and fully stirred for 4-6 hours. Finally, aluminum oxide is added and high-shear emulsification is performed for 5-10 minutes, and then matured for 8-16 hours to obtain the desired modified epoxy resin glue.

[0101] Example 2-3

[0102] The only difference between Example 2-3 and Example 1 is that the amounts of bisphenol A type benzoxazine resin and bisphenol A type cyanate resin are different. The specific amounts are shown in Table 2. The other conditions and parameters are the same as those in Example 1.

[0103] Comparative Example 1

[0104] The only difference between Example 1 and Example 1 is that the amounts of bisphenol A type benzoxazine resin and bisphenol A type cyanate resin are different. The specific amounts are shown in Table 2. The other conditions and parameters are the same as those in Example 1.

[0105] Comparative Example 2

[0106] The difference between Comparative Example 1 and Example 1 is that bisphenol A type benzoxazine resin and bisphenol A type cyanate resin are not added, the amount of epoxy resin added is 100 g, and the other conditions and parameters are the same as those of Example 1.

[0107] Effect Example 1

[0108] (1) Test method for glass transition temperature (dry Tg)

[0109] Use DSC thermal analyzer for testing. Place the sample in the DSC tester and start the test. The instrument will pop up an analysis window. When the analysis is completed, analyze the results and select two analysis points on the relatively smooth and horizontal baseline before and after the curve for analysis.

[0110] (2) Test method for thermal stress tin drift

[0111] The test was conducted using IPC standards, with a test temperature of 288°C, a test interval of 10s, and visual inspection showed that the test was qualified.

[0112] Heat the tin melting furnace to 288±2℃ and maintain a constant temperature. Place the cut samples with the copper foil side facing down on the solder surface and place them for the standard time.

[0113] (3) Test method for thermal stress tin immersion

[0114] The test was conducted using IPC standards, with a test temperature of 288°C, a test interval of 10s, and visual inspection showed that the test was qualified.

[0115] Heat the tin melting furnace to 288±2℃ and maintain a constant temperature. Immerse the cut samples in the solder and place them for the standard time.

[0116] Table 2

[0117]

[0118] It can be seen from Table 2 that the modified epoxy resin of the present application has good thermal stability and high Tg, and can meet the use requirements in high temperature environments; in addition, the modified epoxy resin of the present application also has excellent brittleness and comprehensive performance.

Claims

1. A modified epoxy resin, characterized in that: Its raw materials include epoxy resin, benzoxazine resin and cyanate resin, curing agent and catalyst; Wherein, the mass ratio of the epoxy resin, the benzoxazine resin and the cyanate resin is 6:(1-3):(1-3); Wherein, the mass ratio of the curing agent to the epoxy resin is (0.02-0.05): 1; Wherein, the mass ratio of the catalyst to the epoxy resin is (0.001-0.005):

1.

2. The modified epoxy resin according to claim 1, characterized in that It meets one or more of the following conditions: (1) The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, resorcinol epoxy resin, polyethylene glycol epoxy resin, brominated epoxy resin, isocyanate modified epoxy resin, rubber modified epoxy resin, glycidylamine type epoxy resin and phosphorus-containing epoxy resin; for example, bisphenol A epoxy resin; (2) The benzoxazine resin is selected from one or more of bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, MDA benzoxazine resin, DCPD benzoxazine resin, phenol benzoxazine resin, DOPO benzoxazine resin, phenolphthalein benzoxazine resin, bisphenol AF benzoxazine resin, furfurylamine benzoxazine resin and aniline benzoxazine resin; for example, bisphenol A benzoxazine resin; (3) The cyanate ester resin is selected from bisphenol A cyanate ester resin; (4) The curing agent is selected from one or more of dicyandiamide (DICY), m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, dichlorodiaminodiphenylmethane, phenol novolac resin, bisphenol A novolac resin, phosphorus-containing phenolic resin, benzoxazine resin, xylene formaldehyde resin, urea-formaldehyde resin, modified phenolic resin, maleic anhydride and styrene maleic anhydride copolymer, such as dicyandiamide; (5) The catalyst is selected from one or more of imidazole compounds, benzyldimethylamine, 2,4,6-tris(dimethylaminomethylamine)phenol, and boron trifluoride; Wherein, the imidazole compound is, for example, 2-methylimidazole; (6) The mass ratio of the epoxy resin, the benzoxazine resin and the cyanate resin is (6:3:1), (3:1:1) or (6:1:3); (7) The mass ratio of the curing agent to the epoxy resin is 0.035:1; (8) The mass ratio of the catalyst to the epoxy resin is 0.002:1; (9) The raw materials of the modified epoxy resin also include inorganic fillers and / or organic solvents; (10) The modified epoxy resin is in the form of glue.

3. The modified epoxy resin according to claim 2, characterized in that It meets one or more of the following conditions: (1) The inorganic filler is selected from one or more of silicon dioxide, calcium oxide, magnesium oxide, aluminum oxide, boron oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, talc, calcium carbonate, mica powder, kaolin, magnetic powder and quartz powder, such as aluminum oxide; (2) The mass ratio of the inorganic filler to the epoxy resin is (0.3-0.7):1, for example, 0.5:1; (3) The organic solvent is selected from one or more of acetone, butanone, N,N-dimethylformamide, ethylene glycol methyl ether, and propylene glycol methyl ether, such as N,N-dimethylformamide; (4) The mass ratio of the organic solvent to the epoxy resin is (0.5-0.8):1, for example, 0.67:

1.

4. The modified epoxy resin according to claim 1, characterized in that In parts by mass, the raw materials of the modified epoxy resin include the following formula or are composed of the following formula composition: 60 parts of epoxy resin, 10-30 parts of benzoxazine resin, 10-30 parts of cyanate resin, 1-3 parts of curing agent, Catalyst 0.05-0.2 parts, More preferably, the raw materials of the modified epoxy resin include the following formula or are composed of the following formula in parts by mass: composition: 60 parts of bisphenol A epoxy resin, 10-30 parts of bisphenol A type benzoxazine resin, 10-30 parts of bisphenol A cyanate resin, 1-3 parts of curing agent, Catalyst 0.05-0.2 parts; More preferably, the raw materials of the modified epoxy resin include the following formula or are composed of the following formula in parts by mass: composition: 60 parts of bisphenol A epoxy resin, 10-30 parts of bisphenol A type benzoxazine resin, 10-30 parts of bisphenol A cyanate resin, 1-3 parts of curing agent, Catalyst 0.05-0.2 parts, 20-40 parts of inorganic filler, 20-40 parts of organic solvent.

5. The modified epoxy resin according to claim 1, characterized in that In terms of mass fraction, the raw materials of the modified epoxy resin and the usage ratio thereof are selected from one of the following schemes: Solution 1: 60 parts of bisphenol A epoxy resin, 30 parts of bisphenol A type benzoxazine resin, 10 parts of bisphenol A cyanate resin, 2.1 parts of dicyandiamide, 0.12 parts of 2-methylimidazole, 30 parts of aluminum oxide, 40 parts of N,N-dimethylformamide; Option 2: 60 parts of bisphenol A epoxy resin, 20 parts of bisphenol A type benzoxazine resin, 20 parts of bisphenol A cyanate resin, 2.1 parts of dicyandiamide, 0.12 parts of 2-methylimidazole, 30 parts of aluminum oxide, 40 parts of N,N-dimethylformamide; Option 3: 60 parts of bisphenol A epoxy resin, 10 parts of bisphenol A type benzoxazine resin, 30 parts of bisphenol A cyanate resin, 2.1 parts of dicyandiamide, 0.12 parts of 2-methylimidazole, 30 parts of aluminum oxide, 40 parts of N,N-dimethylformamide.

6. A method for preparing a modified epoxy resin, characterized in that: It includes the following steps: Mixing raw materials for preparing the modified epoxy resin, wherein the raw materials include epoxy resin, benzoxazine resin, cyanate resin, curing agent and catalyst; Wherein, the mass ratio of the epoxy resin, the benzoxazine resin and the cyanate resin is 6:(1-3):(1-3); Wherein, the mass ratio of the curing agent to the epoxy resin is (0.02-0.05): 1; Wherein, the mass ratio of the catalyst to the epoxy resin is (0.001-0.005):

1.

7. The method for preparing the modified epoxy resin according to claim 6, wherein: It meets one or more of the following conditions: (1) The types and amounts of the epoxy resin, the benzoxazine resin, the cyanate resin, the curing agent and the catalyst are as described in any one of claims 2 to 5; (2) The raw materials also include inorganic fillers and / or organic solvents; Preferably, the type and amount of the inorganic filler and / or organic solvent are as described in any one of claims 2 to 5; (3) In the raw materials, the curing agent and the catalyst are in a dissolved state; (4) The mixing is stirring, for example, stirring for 4-6 hours; (5) The preparation method further comprises: after mixing the epoxy resin, the benzoxazine resin, the cyanate resin, the curing agent and the catalyst, adding an inorganic filler, high shear emulsification and aging; Wherein, the high shear emulsification time is, for example, 5-10 minutes; Wherein, the aging time is, for example, 8-16 hours; (6) The modified epoxy resin exists in the form of glue.

8. A modified epoxy resin, characterized in that The modified epoxy resin is prepared by the preparation method of the modified epoxy resin according to claim 6 or claim 7.

9. Use of the modified epoxy resin according to any one of claims 1 to 5 or claim 8 in the preparation of copper clad laminates.

10. The use according to claim 9, characterized in that The method for preparing a copper clad laminate comprises the following steps: The modified epoxy resin as described above is coated on a glass fiber cloth, and after being subjected to baking and pressing processes, a copper clad laminate is obtained; Preferably, the mass per square meter of the glass fiber cloth is 40-300 g / m 2 ; Preferably, the glass fiber cloth is electronic grade glass fiber cloth.

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